Process for breaking petroleum emulsions employing certain oxyalkylated polyepoxide-treated amine-modified thermoplastic phenol-aldehyde resins



United States Patent PROCESS FOR BREAKING PETROLEUM EMUL- SIONSEMPLOYING CERTAIN OX'YALKYLATED presented in considerable detail, yetthe description becomes somewhat involved and certain facts should be2,771,425 Patented Nov. 20, 195,6

POLYEPOXIDE -TREATED AMINE -MODIFIED linking radicals. Our preference isthat either diphenyl THERMOPLASTIC PHENOL-ALDEHYDE RESINS compounds beemployed or else compounds where the divalent link is obtained by theremoval of a carbonyl gig gfifif fizpgg gggg s jgs g if sd ggfizj oxygenatom as derived from a ketone or aldehyde. I

Wilmington, Del a corporation of Delaware If it were not for the expenseinvolved in preparln g and purifying the monomer we would prefer it toany N0 Drawing. f Pp J1me 1953, other form, i. e., in preference to thepolymer or mixture Sena! 364,501 of polymer and monomer.

Stated another way, we would prefer to use materials 20 Clalm's' (Cl.252 338) of the kind described, for example, in U. S. Patent No.

The present invention is a continuation-in-part of our 2,530,353, datedNovember 14, 1950- Said Patent co-pending application, Serial No.338,573, filed February scribes compounds having the general formula 24,1953. X

Our invention provides an economical and rapid process for resolvingpetroleum emulsions of the water-in-oil H29 R type that are commonlyreferred to as cut oil, roily oil, emulsified oil, etc., and whichcomprise fine I 2 droplets of naturally occurring waters or brinesdispersed wherein R is an aliphatic hydrocarbon bridge, each n in a moreor less permanent state throughout the oil independently has one of thevalues 0 and 1, and X is an which constitutes the continuous phase ofthe emulsion. alkyl radical containing from 1 to 4 carbon atoms.

It also provides an economical and rapid process for The compoundshaving two oxirane rings and emseparating emulsions which have beenprepared under ployed for combination with the reactive amine-modifiedcontrolled conditions from mineral oil, such as crude phenolaldehyderesin condensates as herein described are oil and relatively soft watersor weak brines. Controlled characterized by the following formula andcogenerically emulsification and subsequent demulsification under theassociated compounds formed ill their P p H o C/ -\CC OR -1[R]n'R1OC C3C -OR1''[ ]nR10-CCL O Hg H H1 H2 l H2 H: H H! on 4 conditions justmentioned are of significant value in rein which R represents a divalentradical selected from moving impurities, particularly inorganic salts,from pipethe class of ketone residues formed by the elimination lineoil. of the ketonic oxygen atom and aldehyde residues ob- The presentinvention is concerned with the breaking tained by the elimination f h lhy i Yg 310m, of emulsions of the water-in-oil type by subjecting themthe divalent radical to the action of products obtained by a three-stepmanu- H H facturing method involving (1) condensing certain phenol 1375faldehyde resins, hereinafter described in detail, with certain basicnon-hydroxylated secondary monoamines, herethe dlvalent inafterdescribed in detail, and formaldehyde; (2) oxyal- 0 kylation of thecondensation product with certain phenolic g polyepoxides, hereinafterdescribed in detail; and (3) oxyalkylation of the previouslyoxyalkylated resin condenradlcal the dwflent Sulfone and divalent satewith certain monoepoxides, also hereinafter described monosulfideradical the dlvalent radlcal in detail. 1 -CH2SCH2 to 22 i g g gf :23;gg' ljggi g i: 33:23:; and the divalent disulfide radical S-S and R10 isdiepoxides or the low molal polymers one usually obtains the divalentradical obtamed by the ehmmation of a hydroxyl hydrogen atom and anuclear hydrogen atom co-generic materials which may includemonoepoxides. from the henol However, the cogeneric mixture isinvariably characterized P by the fact that there is on the average,based on the OH molecular weight, of course, more than one epoxide groupper molecule.

A more limited aspect of the present invention is represented by the useof such products wherein the I polyepoxide is represented by (1)compounds of the mwhlch B" and Rm representhydmgen and hydro followingformula; carbon substltuents of the aromatic nucleus, said substituentmember having not over 18 carbon atoms; n

H2G-CHCHr-QC represents an integer including zero and 1 and n representsa whole number not greater than 3. The above 6 mentioned compounds andthose cogenerically associated and coaenerleally associated coinpoundsfolimed compounds formed in their preparation are thermoplastic i P eP QPreceding, With the R Q Q that andorganic solvent soluble. Reference tobeing thermo- It consists Principally of the monomer as distinguishedplastic characterizes products as being liquids at ordinary from othercogellelstemperature or readily convertible to liquids by merelyNotwithstanding the fact h s q ent t W h 7 0 heating below the point ofpyrolysis and thus differentiates them from infusible resins. Referenceto being soluble in an organic solvent means any of the usual organic Ibility represents an anhydro base or the free base (com- 2,771,425 .3solvents, such as alcohols, ketones, esters, ethers, mixed solvents,etc. Reference to solubility is merely to differ- 4 xylene. If xylenealone does not serve then a mixture of xylene and methanol, forinstance, 80 parts of xylene and entiate from a reactant which is notsoluble and might be 20 parts of methanol, or 70 parts of xylene and 30parts of not only insoluble but also infusible. Furthermore,solumethanol, can be used. Sometimes it is desirable to add bility is afactor insofar that it is sometimes desirable to 5 a small amount ofacetone to the xylene-methanol mixdilute the compound containing theepoxy rings before ture, for instance, 5% to of acetone. reacting withthe amine resin condensate. In such in- A mere examination of the natureof the products bestances, of course, the solvent selected would have tobe fore and after treatment with the polyexpoxide reveals one which isnot susceptible tooxyalkylation, as, for ex. that the polyepoxide by andlarge introduces increased ample, kerosene, benzene, toluene,'dioxane,various ke- 10 hydrophobe character or, inversely, causes a decrease intones, chlorinated solvents, dibutyl ether, dihexyl ether,ethyleneglycol diethylether, diethyleneglycol diethylether, istics ofthe final product i. e., the product obtained by anddimethoxytetraethyleneglycol. oxyalkylation of a monoepoxide, may varyall over the 'The expression epoxy is not usually limited to the map.This is perfectly understandable because ethylene 1,2-epoxy ring. The1,2-epoxy ring is sometimes reoxide, glycide, and to a lesser extentmethyl glycide, inferred to as the oxirane ring to distinguish it fromother troduce predominantly hydrophile character, while proepoxy'rings.Hereinafter the word epoxy unless inpylene oxide and more especiallybutylene oxide, introd icated otherwise, will be used to mean theoxirane ring, duce primarily hydrophobe character. A mixture of the i.e., the 1,2-epoxy ring. Furthermore, where a comvarious oxides willproduce a balancing in solubility charpound has two or more oxiranerings they will be reacteristics or in the hydrophile-hydrophobecharacter so ferred to as polyexpodies. They usually represent, of astobe about the same as prior to oxyalkylation with the course,1,2-epoxide rings or oxirane rings in the alphamonoexpoxide. omegaposition; This is a departure, of course, from the As far as the use ofthe herein described products goes standpoint of strictly formalnomenclature as in the exfor purpose of resolution of petroleumemulsions of the ample of the simplest diepoxide which contains at leastwater-in-oil type, we particularly prefer to use those which 4 carbonatoms and is formally described as 1,2-epoxyas such or in the form ofthe free base or hydrate, i. e., 3,4'-epoxybutane (1,23,4diepoxybutane). combination with water or particularly in the form of aHaving obtained a reactant having generally 2 epoxy 10W molal organicacid salt such as the gluconates or the rings as depicted in the lastformula preceding, or low acetate or hydroxy acetate, have suflicientlyhydrophile molal polymers thereof, it becomes obvious the reactioncharacter to at least meet the test set forth in U. S. can take placewith any amine modified phenol-aldehyde Patent No. 2,499,368, datedMarch 7, 1950, to De Groote resin by virtue of the fact that there arealways present etal. In said patent such test for emulsification using areactive hydroxyl groups which are part of the phenolic water-insolublesolvent, generally'xylene, is described as nuclei and theremay bepresent reactive hydrogen atoms an indexof surface activity. attached toa nitrogen atom, or an oxygen atom, depend- H In the present instancethe various condensation proding on the presence of a hydroxylated groupor seconducts as such or in the form of the free base or in the form aryamino group. "of the acetate, may not necessarily by xylene-soluble Toillustrate the products which represent the subject although y are in yinstances- If Such Compounds matter of the present invention referencewill be made are not xylene-soluble the obvious chemical equivalent orto a reaction involving a mole of the oxyalkylating agent, 40 equivalentchemical test can be made by simply using i. e., the compound having 2oxirane rings and an amine condensate. Proceeding with the examplepreviously de-' scribed it is obvious the reaction ratio of 2 moles ofthe amine condensate to one mole of the oxyalkylating agent gives aproduct which may be indicated as follows: v,

, such as ethylene glycol diethylether, or a low molal alcohol, or amixture to dissolve the appropriate product bein which the variouscharacters have their previous significance and the characterizationcondensate is simply an abbreviation for the' condensate which isdescribed in presence manifest. It is understood the reference in thegreater detail subsequently. hereto appended claims as to the use ofxylene in the Such intermediate product in turn also must be solubleemulsification test includes such obvious variant. but solubility is notlimited to an organic solvent but may For purpose of convenience what issaid hereinafter include water, or for that matter, a solution of waterconwill be divided into nine parts with Part 3, in turn, being tainingan acid such as hydrochloric acid, acetic acid, hydivided into threesubdivisions: droxyacetic acid, etc. In other words, the nitrogen groupsPart 1 is concerned with our preference in regard to the present,whether two or more, may or may not be signipolyepoxide and particularlythe diepoxide reactant; ficantly basic and it is immaterial whetheraqueous solu- Part 2 is concerned with certain theoretical aspects ofdiepoxide preparation;

Part 3, Subdivision A, is concerned with the preparation of monomericdiepoxides, including Table I;

Part 3, Subdivision B, is concerned with the preparation of low molalpolymeric epoxides or mixtures con- (condensate phases on vigorousshaking and surface activity makes its bination with water (or a saltform which is the acetate, chloride, etc. The purpose in this instanceis to diiferentiate from insoluble resinous materials, particularlythose resulting from gelation or cross-linking. Not only does thisproperty serve to differentiate from instances where an insolublematerial is desired, but also serves to monomer and includes Table II;

emphasize the fact that in many instances the preferred Part 3,Subdivision C, is concerned with miscellaneous compounds have distinctwater-solubility or are distinctly phenolic reactants suitable fordiepoxide preparation; dispersible in 5% gluconic acid. For instance,the prod- Part 4 is concerned with the phenol-aldehyde resin ucts freedfrom any solventcan be shaken with 5 to 20 times their weight of 5%gluconic acid at ordinary temtion to yield the amine-modified resin;perature and show at least some tendency towards being 'Part 5 isconcerned with appropriate basic secondary self-dispersing. The solventwhich is generally tried is amines free from a hydroxyl radical whichmay be emhydrophile character. However, the solubility character-' somesuitable solvent, preferably a water-soluble solvent I ing examined andthen mix with the equal weight of xylene, followed by addition of water.Such test is ob viously the same for the reason that there will be twotaining low molal polymeric epoxides as well as the a which is subjectedtomodification by condensation reac ployed in the preparation of theherein-described aminemodified resins; V

Part 6 is concerned with reactions involving the resin, the amine, andformaldehyde to produce specific products or compounds which are thensubjected to reaction with polyepoxides;

Part 7 is concerned with the reactions involving the two preceding typesof materials and examples obtained by such reaction. Generally speaking,this involves nothing more than a reaction between 2 moles of apreviously prepared amine-modified phenol-aldehyde resin condensate asdescribed, and one mole of a polyepoxide so as to yield a new and largerresin molecule, or comparable product;

Part 8 is concerned with the use of a monoepoxide in oxalkylating theproducts described in Part 7, preceding, i. e., those derived by meansof reaction between a polyepoxide and an amine-modified phenol-aldehyderesin as described;

Part 9 is concerned with the resolution of petroleum emulsions of thewater-in-oil type by means of the previously described chemicalcompounds or reaction products.

PART 1 As will be pointed out subsequently, the preparation ofpolyepoxides may include the formation of a small amount of materialhaving more than two epoxide groups per molecule. If such compounds areformed they are perfectly suitable except to the extent they may tend toproduce ultimate reaction products which are not solventsoluble liquidsor low-melting solids. Indeed, they tend to form thermosetting resins orinsoluble materials. Thus, the specific objective by and large is toproduce diepoxides as free as possible from any monoepoxides and as freeas possible from polyepoxides in which there are more than two epoxidegroups per molecule. Thus, for practical purposes what is saidhereinafter is largely limited to polyepoxides in the form ofdiepoxides.

As has been pointed out previously one of the reactants employed is adiepoxide reactant. It is generally obtained from phenol(hydroxybenzene) or substituted phenol. The ordinary or conventionalmanufacture of the epoxides usually results in the formation of aco-generic mixture as explained subsequently. Preparation of the monomeror separation of the monomer from the remaining mass of the co-genericmixture is usually expensive. If monomers were available commercially ata low cost, or if they could be prepared without added expense forseparation, our preference would be to use the monomer. Certain monomershave been prepared and described in the literature and will be referredto subsequently. However, from a practical standpoint one must weigh theadvantage, if any, that the monomer has over other low molal polymersfrom a cost standpoint; thus, we have found that one might as wellattempt to prepare a monomer and fully recognize that there may bepresent, and probably invariably are present, other low molal polymersin comparatively small amounts. Thus, the materials which are most aptto be used for practical reasons are either monomers with some smallamounts of polymers present or mixtures which have a substantial amountof polymers present. Indeed, the mixture can be prepared free frommonomers and still be satisfactory. Briefly, then, our preference is touse the monomer or the monomer with the minimum amount of higherpolymers.

It has been pointed out previously that the phenolic nuclei in theepoxide reactant may be directly united, or united through a variety ofdivalent radicals. Actually, it is our preference to use those which arecommercially available and for most practical purposes it meansinstances where the phenolic nuclei are either united directly withoutany intervening linking radical, or else united by a-ketone residue orformaldehyde residue. The commercial bis-phenols available now in theopen market il- 6 lustrate one class. The diphenyl derivativesillustrate a second class, and the materials obtained by reactingsubstituted monofunctional phenols with an aldehyde illustrate the thirdclass. All the various known classes may be used but our preferencerests with these classes due to their availability and ease ofpreparation, and also due to the fact that the cost is lower than inother examples.

Although the diepoxide reactants can be produced in more than one way,as pointed out elsewhere, our preference is to produce them by means ofthe epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains onlya modest amount of polymers corresponds to the derivative of bis-phenolA. It can be used as such, or the monomer can be separated by an addedstep which involves additional expense. This compound of the followingstructure is preferred as the epoxide reactant and will be used forillustration repeatedly with the full understanding that any of theother epoxides described are equally satisfactory, or that the higherpolymers are satisfactory, or that mixtures of the monomer and higherpolymers are satisfactory. The formula for this compound is Referencehas just been made to bis-phenol A and a suitable epoxide derivedtherefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2isomers being present. It is immaterial which one of these isomers isused and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, towit, Part1, and in succeeding parts, the text is concerned almostentirely with epoxides in which there is no bridging radical or thebridging radical is derived from an aldehyde or a ketone. It would beimmaterial if the divalent linking radical would be derived from theother groups illustrated for the reason that nothing more than meresubstitution of one compound for the other would be required. Thus, whatis said hereinafter, although directed to one class or a few classes,applies with equal force and effect to the other classes of epoxidereactants.

If sulfur-containing compounds are prepared they should be freed fromimpurities with considerable care for the reason that any time that alow-molal sulfurcontaining compound can react with epichlorohydrin theremay be formed a by-product in which the chlorine happened to beparticularly reactive and may represent a product, or a mixture ofproducts, which would be unusually toxic, even though in comparativelysmall con-- centration.

PART 2 The polyepoxides and particularly the diepoxides cans be derivedby more than one method as, for example, theuse of epichlorohydrin orglycerol dichlorohydrin. If a product such as bis-phenol A is employedthe ultimate: compound in monomeric form employed as a reactant in: thepresent invention has the following structure:

Treatment with epichlorohydrin, for example, does not yield this productinitially but there is an intermediate produced which can be indicatedby the following structure:

reaction? Actually, what may happen for any one of number of reasons isthatone o btains a product in which there is only oneepoxide ring andthere may, as a matter of fact, b i fi h h s ii l sh h ias hlst at d hth h l th' hh hi i (2) Even if one starts with the reactants in thepreferred ratio, to wit, two parts oflepichlorohydrin to one part ofbisphenol A, they do not necessarily so react and as 'a result"one"rna'yobtain'products in which'more than two epichlor'ohydrin residues becomeattached to a'singl'e bis-phenol A nucleus by virtue of the reactivehydroxyls present which enter into oxylalkylation' reactions rathertha'ririug closure'reactions;

('3) 'As is well known; ethylene oxide in the presence of alkali, andfor that matter in the complete absence'of water,- 1 forms cyclicpolymers. Indeed, ethylene oxide canproducea'solid'polymer: This samereaction can, and at times apparently does, take place" in connectionwith compounds "having one, or'in'the present instance, two substituted'oxirane rings, i. e'., substituted 1,2 epoxy rings; Thus; in many waysit is easier to produce a poly mer,-particularly"a mixture of themonomer, dimer and trimer,*than it is to produce the monomer alone.

"(4) As has been'pointed out previously, monoepoxides (IJ QH! n' C I 05/CH. O O O .1

I I OH: H H H H H H -s C ?C a 0H3 i o may react with a mole ofbis-phenol A to give a monoepoxy structure. Indeed, in the subsequenttext immediately following reference is made to the dimers,

rimsh tr hs hwh hhi We hhxi la h s. present. Needless to say, compoundscan be formed,

which correspond in every respect except that one terminal epoxide groupis absent and in its place is a group having one'chlorine atomand onehydroxyl group, or else two hydroxyl groups, o -fan unreacted phenplicl,ring.

. (5..) ome reference has be n made t h p e. f a chlorine atom andalthough all effortflisldirectedutothe elimination of any,chlorine-coutainingmoleu ciye t is apparent tha is often an i e l pprather than a practical possibility. Indeed, the same sort of reactantsare sometimes employed to obtain products in w i h nten on ly h re sboth an p i gr p and a chlorine atom present. See .U. S. Patent No;2,581,464, dated January 8, 1952, to Zech.

What has been said in regard to the theoretical aspect is, of course,closely related to the actual method of preparation which is discussedin greater detail in Part 3, particularly Subdivisions A and B. Therecanv be no clear line between the theoretical aspect and actualpreparative steps. However, in order to summarize or illustrate whathasbeen said in Part 1, immediately preceding reference will be made toa typical example which already has been employed for purpose ofillustration. The particular example is i HQ QTOTC, TCH

I 0 OH; 0

It is obvious that two molesof such material combine readily with onemole of bis-phenol A, 3

. 0 11,. to produce the, product which is one step further along,

at least, towards polymerization. In other words, one".

products available "under'the name of Epon Resins as now sold in theopen'market. 'Se'c also, chemicalpamphlet entitled Epon Surface-CoatingResins, Shell Chemi cal Corporation, New York city. The word Epon is a ser esms h of Sh l C emi a s at h For, thepurpose ofitheinstantinvention, n, mayrepresent ajnumber including zero, and at the most,v alow.

number such as l, 2 or3. This limitation, does not exist in actualefforts to obtain resins as diiferentiated from the herein describedsoluble materials. It is quite probable that in the resinous products asmarketed for coating use the value of rtf 'is usually substantiallyhigher. I Note again what has been said previously that any formulaisf'a't best,"an"over-simplif cation, or at the most repre sents perhapsonly themore irnportant or principal constituent or constituents. Thesematerials may'vary from simple non-resinous to, complex resinousepoxides which hy rwsyl hups,

Referring now. to. what hasbeen said' previously, to

wit,.compounds having both an epoxy ring oi'rthe c'qu'i'va-- 9 lent andalso a hydroxyl group, one need go no further or for greater simplicitythe formula could be restated thus:

H: ER

than to consider the reaction product of and bisphenol A in amole-for-mole ratio, since the initial reactant would yield a producthaving an unreacted epoxy ring and two reactive hydroxyl radicals.Referring again to a previous formula, consider an example where twomoles of bisphenol A have been reacted with 3 moles of epichlorohydrin.The simplest compound formed would be th III in which R, R", and R'represent a member of the class consisting of hydrogen and hydrocarbonsubstituents us of the aromatic nucleus, said substituent member havingnn, m on,

C CH1 Such a compound is comparable to other compounds havnot over 18carbon atoms; n represents an integer ing both the hydroxyl and epoxyring such as 9,10-epoxy selected from the class of zero and 1, and nrepresents octadecanol. The ease with which this type of compoundpolymerizes is pointed out by U. S. Patent No. 2,457,329, dated December28, 1948, to Swern et al.

The same difiiculty which involves the tendency to polymerize on thepart of compounds having a reactive ring and a hydroxyl radical may beillustrated by com pounds where, instead of the oxirane ring (1,2-epoxyring) there is present a 1,3-epoxy ring. Such compounds are derivativesof trimethylene oxide rather than ethylene oxide. See U. S. Patents Nos.2,462,047 and 2,462,048,

both dated February 15, 1949, to Wyler. I

At the expense of repetition of what appeared previously, it may be wellto recall that'these materials may vary from simple soluble non-resinousto complex nonsoluble resinous epoxides which are polyether derivativesa whole number not greater than 3.

PART 3 Subdivision A The preparations of the diepoxy derivatives of thediphenols, which are sometimes referred to as diglycidyl ether-s, havebeen described in a number of patents. For convenience, reference willbe made to two only, to wit, aforementioned U. S. Patent 2,506,486, andaforementioned U. S. Patent No. 2,530,353.

Purely by Way of illustration, thefollowing diepoxides, or diglycidylothers as they are sometimes termed, are included for purpose ofillustration. These particular compounds are described in the twopatents just mentioned.

TABLE I Ex- Patent ample Diphenol Dlglycidyl ether refernumber ence CH;CsH4OH); D1(epoxypropoxyphenyl)methane CH; H(C@H4OH)1D1(epoxypropoxyphenyl)methylmethane (CH3)1C(CH4OH):Di(epoxypropoxyphenyl)dimethylmethane- OgHsC (OH!) (ODiepoxypropoxyphenyl)ethylmethylmothane 2, 506, 486 (CgH5)2C (CQH4 Dlepoxypropoxyphenyl)diethylmethane 2, 506, 486 CH;O(C;H1)(O5H4OH)1Dl(epoxypropoxyphenyl)methylpropylmethane. 2, 506, 486 CHsC (C (CUH4OH),Dl(epoxypropoxyphenyl)methylphenylmothene 2, 506, 486 O HsCDi(epoxypropoxypheuyl)ethylphenylmethane 2, 506, 486 CaH1C( gs)(CsH4OH); i(epoxypropoxyphenyl)propylphcnylmethane. 2, 506, 486O4H.C(OH5) (CsHAOH): Dlgepoxypropoxyphenyl)butylphonylmcthano. 2, 506,486 (OHsG Di epoxypropoxyphenyl)tolylmethane 2, 506, 486 (CH;C@H4)O(OH;)(0.1140 Dl(epoxypropoxyphenyl)tolylmethylmethane 2. 506, 486 ihy4,4'-bls(2,3-epoxypropoxy)diphenyl 2, 530, 353 (CH1)2,2-bis(4-(2,3-epoxypropoxy) 2-tertierybutyl phenyl))propnne 2, 530, 353

of polyhydric phenols containing an average of more than one epoxidegroup per molecule and free from functional groups other than epoxideand hydroxyl groups. The former are here included, but the latter, i.e., highly resinous or insoluble types, are not.

In summary then in light of what has been said, compounds suitable forreaction with amines may be summarized by the following formula:

' H1 H H; H l t...

Subdivision B As to the preparation of low-molal polymeric epoxides ormixtures reference is made to numerous patents and particularly theaforementioned U. S. Patents Nos. 2,575,558 and 2,582,985.

In light of aforementioned U. S. Patent No. 2,575,558, the followingexamples can be specified by reference to the formula therein providedone still bears in mind it is in essence an over-simplification.

TABLE 11 (continued) Example R O from HR H R n 1: Remarks number 319Dlbntylphe'nol (ortho-pare). g 101 1 0,1,2 See prior note.

. I H H 320.--.-. -.do H H 1 0,1,2 D0.

1321.--..- DinonylphenoKortho-para). 13 I61 1 0,1,2 Do.

a H H B22 Hydroxybenzene (H) 1 0,1,2 D0.

1323;; dn Nona 0 o, 1, 2 Do.

324.-.-1. OrthorisopropyI phenol CH3 1 0,1,2 See prior note. As toreparation 014,4-

- isopropylidene bls- 2-lsopropylphenol) see U. 8. Patent No. 2,482,748,dated 1 Sept. 27, 1949, to Dietzler. CH3

B25 Para-cot 1 bone! CH SCH 1 0,1 2 See prior note. (As to preparationortho y p r. 2 phenol sulfide see U. S. Patent'No. 2,488,134, dated Nov.15, 1949, to I Mlkeska et a1.)

B26 H dro benzene OH 1 0,1 2 See priornote. (Asto pro eration ottha y xys phenol sulfide see U. Patent No. 2,526,545.)

ill: I CgHs Subdivision C Other samples include:

The prior examples have been limited largely to those 9 in which thereis no divalent linking radical, as in the case of diphenyl compounds, orwhere the linking radical 40 is derived from a ketone or aldehyde,particularly a ketone. Needless to say, the same procedure isemployed inconverting diphenyl into a diglycidyl ether regardless of the nature ofthe bond between the two phenolic nuclei.

OH: OH: For purpose of illustration attention is directed to wherein R1is a substituent selectedfrom the class con-;

sisting of secondary butyl and tertiary butyl groups and I h v s vmerous other dlp enols whlch can be readfly converted R2 1s asubstituent selected from the classeonsisting of to a suitablepolyepoxide, and particularly diepoxide,

alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups, and reactant i 1 iv wherein said alkyl group contains at least 3 carbon- As previouslypointed out the imtial phenol may be atoms SeeU S'Patent No 2 515 907substituted, and the substituent group in turn may be a e i cyclic groupsuch as the phenyl group or cyclohexyl group Hm as in the instance ofcyclohexylphenol or phenylphenol; O H H Such substituents are usually inthe ortho position and n may be illustrated by a phenol of the followingcomposi- 5 tion: 5

v GsH l CaHu in which the C5H11"g roups are secondary amyl groups.

E See U. s. Patent No. 2,504,064.

(1 CeHn /Oo n HO OH HO OH See U. s. Patent No. 2,285,563.

11 "on; H on. 0111-6-03 Similar phenols which are monofunctional, forinstance, OH: paraphenyl phenol or par-acyclohexyl phenol with anadditional substituent in the ortho position, may be em- OH: ployed' inreactions previously referred to, for instance, I with-formaldehyde orsulfur chlorides to give comparable g phenolic compounds having 2hydroxyls and suitable to v 0H; CH:

subsequent reaction with epichlorohydrin, etc. 76

See U. S. Patent No. 2,503,19

wherein R1 is a substituent selected frQInt-he .cljass consisting ofsecondary butyl and tertiary butyl" groups and R2 is a substituentselected frqrntheclass consisting ofalkyL.

cycloalkyl, aryl, aralkyl, andsalkaryl groupst. U; S. Patent No.2,515,906. 1 a

HaC(|3-U H:

See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

Q- G H p on See U. Si PatentNo. 2,331,448;

. kyl I in which R5 is a methyleneradical, .orazsubstituted methyleneradical which.represents- ,th e residueofian aldehyde and is preferablythe unsubstitutedmethylene radical de rived from formaldehyde. See-U18:Pfatent No. 2.,430Q002;

See also U; S. PatenuNo. 2,581,919; which describes di(dialky1 cresol)sulfides which, include; the monosulfides, the disulfides, andthepolysulfides. The following formula represents the various dicresolsulfides of this invention:

OH CH: OH: OH

, Bil.

R: R1. R1 R1 in which R1 and R2 are alkylgroups, the sum of whose carbonatoms equals 61o about 20, and R; and R2 each Astoldescriptionsofvarious suitable phenol j'sulfide's,

preferably contain 3 to about 10 carbon atoms, and x is 1'1 to 4. Theterm sulfides as used in this text, therefore, includes monosulfide,disulfide, and polysulfides.

PART 4 It is well known that one can readily purchase on the Y openmarket, or prepare, fusible, organic-solvent-soluble water-insolubleresin polymers of a composition approximatedin an idealized form by theformula on OH B r H o-- 0- v H B? 1 R n: R

In the above formula n represents a small whole number 'varying from 1to 6,, 7- or 8,011 more, up to. probably 1,0 or 12 units, particularlywhen the resin is subjected to heating under a vacuum as described inthe literature. A limited sub-genus is in the instance of low molecularweight polymers: where the total number of phenol nuclei variesfrom 3.to,6,,i. e., n varies from 1, to 4;. R represents an aliphatichydrocarbon substitutent, generally an alkyl radical having from 4 to 15carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical.Where the divalent bridge radical is shown as being'derivedfromformaldehyde it may; of course, be derived from any other reactivealdehydehaving 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it isnecessarily soluble in any organic solvent. This is particularlytruewhere the resins are derived from trifunctional phenols aspreviouslynoted; However, even when obtained from a difuuctional phenol, forinstance paraphenylphenol, one may obtain a resin which is not solublein a nonoxygenated solvent," such as benzene, or xylene, but requires anoxygenated solvent such as a low molol alcoholgdioxane, ordiethyleneglycol diethylether. Sometimes a mixture'of the twosolvents'(-oxygenated and non-oxygenated) will-serve. See Example 9aofU.Si Patent No.- 2,499,365, dated March 7', 1950, to' De' Groote' and-Keiser.

The resins herein employed asrawmaterials must'be soluble in anonoxygenated solvent, such. asbenzeneor xylene. This presents noproblem insofar that all'tliat' is required is to makeasolubility'testl'on commercially available resins, or else prepareresinswhich' are'xylene or benzene-soluble as described inaforementioned"U.. S. Patent' No. 2,499,365, or'in U; S; Patent No;2,499,368, dated March 7, 1950; to DeG'roote and Keisezt' In said patentthere are' described oxyalkylation-susc'eptible," fusible, nonoxygenatedorg'anic solvent=solubl'e," water insoluble, low-stagephenolaldehyde-resin's having an average molecular weight correspondingm m--1easr 3 and not over 6 phenolic nuclei per resin molecule. Theseresins are difunctional only in regard to methylol-forming reactivity,are derived by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and reactivetoward said phenol,and are formed in the substantial absence of trifunctional phenols. Thephenol is of the'formula in-whieh R is, an, aliphatic hydrocarbonradical having, atleastr4 carbon atomsiand. not more-than 24.carbonatoms, and substituted in the2,4',6 position.

If ,one; selected atresin; of; thei-kind ,justdescribedspmviously and.reacted I aproximately one mole/of.-

resin with, two;.moles of pformaldehydenand. two-moles; of; a: basicnonhydroqtylated secondaryamine as .specified,;.fol lowing the sameidealized over-simplification previously referred to, the resultantproduct might be illustrated thus:

The basic nonhydroxylated amine may be designated thus:

As has been pointed out previously, as far as the resin unit goes onecan use a mole of aldehyde other than formaldehyde, such asacetaldehyde, propionaldehyde or butyraldehyde. The resin unit may beexemplified thus:

in which R is the divalent radical obtained from the particular aldehydeemployed to form the resin. For reasons which are obvious thecondensation product obtained appears to be described best in terms ofthe method of manufacture.

As previously stated the preparation of resins, the kind herein employedas reactants, is well known. See previously mentioned U. S. Patent2,499,368. Resins can be made using an acid catalyst or basic catalystor a catalyst having neither acid nor basic properties in the ordinarysense or without any catalyst at all. It is preferable that the resinsemployed be substantially neutral. In other words, if prepared by usinga strong acid as a catalyst, such strong acid should be neutralized.Similarly, if a strong baseis used as a catalyst it is preferable thatthe base be neutralized although we have found that sometimes thereaction described proceeded more rapidly in the presense of a smallamount of a free base. The amount may be as small as a 200th of apercent and as much as a few 10ths of a percent. Sometimes moderateincrease in caustic soda and caustic potash may be used. However, themost desirable procedure in practically every case is to have the resinneutral.

In preparing resins one does not get a single polymer, i. e., one havingjust 3 units, or just 4 units, or just 5 units or just 6 units, etc. Itis usually a mixture; for instance, one approximating 4 phenolic nucleiwill have some trimer and pentamer present. Thus, the molecular weightmay be such that it corresponds to a fractional value for n as, forexample, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins We found no reason for usingother than those which are lowest in price and most readily availablecommercially. For purposes of convenience suitable resins arecharacterized in the following table:

TABLE III M01. wt.

Ex- R of resin ample R Position derived n molecule number of R from-(based on n+2) Phenyl Para. Formal- 3. 5 992. 5

dehyde. Tertiary butyl do. 3. 5 882. 5 Secondary butyl. 3. 5 882. 5Cycle-h 3. 5 1, 025. 5 Tertiary amyl 3. 5 959. 5 Mixed secondary 3. 5805. 5

and tertiary army].

3. 5 l, 148. 5 ony 3. 5 1,456.5 Tertiary butyl 3. 5 1,008. 5

Tertiary amyl 3. 5 1, 085. 5 Nonyl 3. 5 1, 393. 5 Tertiary butyl 4. 2996.6

Tertiary amyl 4. 2 1, 083. 4 Nonyl 4, 2 1, 430. 6 Tertiary butyl. 4.8 1,094. 4 Tertiary amyL. 4. 8 1, 189. 6 ony 4. 8 1, 570. 4 Tertiary amyL.1.5 604.0 Cycle-hexyl. 1. 5 646. 0 H l 1. 5 653.0 1. 5 688.0

PART 5 As has been pointed out previously, the amine herein employed asa reactant is a basic secondary monoamine, and preferably a stronglybasic secondary monoamine, free from hydroxyl groups whose compositionis indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radicaland may be heterocyclic in a few instances as in the case of piperidineand a secondary amine derived from furfurylamine by methylation orethylation, or a similar procedure.

Another example of a heterocyclic amine is, of course, morpholine.

The secondary amines most readily available are, of course, amines suchas dimethylamine, methylethylamine, diethylamine, dipropylamine,ethylpropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine,and dinonylamine. Other amines include bis(1,3-dimethylbutyl)amine.There are, of course, a variety of primary amines which can be reactedwith an alkylating agent such dimcthyl sulfate, diethyl sulfate, an'alkyl bromide, an ester of sulfonic acid ete., to produce suitableamines within the herein specified limitations. For example, one canmethylate alpha-methyl-benzylamine, or benzylamine itself, to produce asuitable reactant. Needless 'to say, one can use secondary amines suchas dicyclohexylamine, dibutylamine or amines containing one cyclohexylgroup and one alkyl group, or one benzyl group and one alkyl group, suchas ethylcyclohexyl amine, ethylbenzylamine, etc. i

Another class of amines which are particularly desirable for the reasonthat they introduce a definite hydrophile effect by virtue of an etherlinkage, or repetitious ether linkage, are certain basic polyetheramines of the formula in which x is a small whole number having a valueof l or more, and may be as much as or 12; n is an integer having avalue of 2 to 4, inclusive; m represents the numeral 1 to 2; and mrepresents a number 0 to 1, with the proviso that the sum of m plus mequals 2; and R has its prior significance particularly as ahydrocarbonradical. Examples include Other somewhat similar secondary amines arethose of the composition as described in U. S. Patent No. 2,375,659dated May 8, 1945, to Jones et al. In the above formula R may be methyl,ethyl, propyl, amyl, octyl, etc.

Other amines can be obtained from products which are sold in the openmarket, such as may be obtained by alkylation of cyclohexylmethylamineor the alkylation of similar primary amines, or, for that matter, aminesof the kind described in U. S. Patent No. 2,482,546, dated September 20,194-9, to Kaszuba, provided there is no negative group or halogenattached to the phenolic nucleus. ethylamine, gamma-phenoxypropylamine,beta-phenoxyalpha-methylethylamine, and beta-phenoxypropylamine.

Other suitable amines are the kind described in British Patent No.456,517 and may be illustrated by The products obtained by the hereindescribed processes employed in the manufacture of the condensationproduct represent cogeneric mixtures which are the result of acondensation reaction or reactions. Since the resin molecule cannot bedefined satisfactorily by formula, although it may be so illustrated inan idealized simplification, it is difficult to actually depict thefinal product of the cogeneric mixture'except in terms of the processitself. I I

Previous reference has been made to the fact that the procedure hereinemployed is comparable, in a general way, to that which corresponds tosomewhat similar derivatives made either from phenols as diflerentiatedfrom a resin, or in the manufacture of a phenol-aminealdehyde resin; orelse from a particularly selected resin and an amine and formaldehyde inthe manner described Examples include the following: be'ta-phenoxyinBruson Patent No. 2,031,557 in order to obtain a heat-reactive resin.Since the condensation products Obtained are not heat-convertible andsince manufacture is not restricted to a single phase system, and sincetemperatures up to C. or thereabouts may be employed, it is obvious thatthe procedure becomes comparatively simple. Indeed, perhaps nodescription is necessary over and above what has been said previously,in light of subsequent examples. However, for purpose of clarity thefollowing details are included. I

A convenient piece or" equipment for preparation of these cogenericmixtures is a resin pot of the kind described in aforementioned U. S.Patent No, 2,499,368. In most instances the resin selected is not apt tobe a fusible liquid at the early or low temperature stage of reaction ifemployed as subsequently described; in fact,

usually it is apt to be a solid at ordinary or higher temperatures, forinstance, ordinary room temperature. Thus, we have found it convenientto use a solvent and particularly one which can be removed readily at acomparatively moderate temperature, for instance at 150 C. A suitablesolvent is usually benzene, xylene, or a comparable petroleumhydrocarbon or a mixture of such or similar solvents. Indeed, resinswhich are not soluble except in oxygenated solvents or mixturescontaining such solvents are not here included as raw materials. Thereaction can be conducted in such a way that the initial reaction, andperhaps the bulk of the reaction, takes place in a polyphase system.However, if desirable, one can use an oxygenated solvent such as alowboiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higheralcohols can be used or one can use a comparatively non-volatile solventsuch as dioxane or the diethylether or ethyleneglycol. One can also usea mixture of benzene or xylene and such oxygenated solvents. Note thatthe use of such oxygenated solvent is not required in the sense that itis not necessary to use an initial resin which is soluble only in anoxygenated solvent as just noted, and it is not necessary to have asingle phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that inmost cases aqueous formaldehyde is employed, which may be the commercialproduct which is approximately 37%, or it may be diluted down to about30% formaldehyde. However, paraformaldehyde can be used but it is moredifiicult perhaps to add a solid material instead of'the liquid solutionand, everything else being equal, the latter is apt to be moreeconomical. In any event, water is present as water of reaction. If thesolvent is completely removed at the end of the process, no problem isinvolved if the material is used for any subsequent reaction. However,if the reaction mass is going to be subjected to some further reactionwhere the solvent may be'objectionable, as in the case of ethyl or hexylalcohol, and if there is to be subsequent oxyalkylation, then,obviously, the alcohol should not be used or else it should be removed.The fact that an oxygenated solvent need not be employed, of course, isan advantage for reasons stated,

Another factor, as far as the selection of solvent goes, is whether ornot the cogeneric mixtureobtained at the end of the reaction is to beused as such or in the salt form. The cogeneric mixtures obtained areapt to be solids or thick viscous liquids in which there is some changefrom the initial resin itself, particularly if some of the initialsolvent is apt to remain without complete removal. Even if one startswith a resin which is almost Water-white in color, the products obtainedare almost invariably a dark red in color or at least a red-amber. orsome color which includes both an amber component and areddishcomponent. By and large, the melting point is apt to be lower and theproducts may be more sticky and more tacky than the original resinitself. Depending on the resin selected and on the amine selected thecondensationproduct or reaction mass on a solvent- -free basis maybehard, resinous and comparable to the resin itself.

The products obtained, depending on'the reactants selected, may bewater-insoluble or water-dispersible, or water-soluble, or close tobeing water-soluble. Water solubility is enhanced, of course, by makinga solution in the acidified vehicle such as a dilute solution, forinstance, a solution of hydrochloric acid, acetic acid, hydroxyaceticacid, etc. One also may convert the finished product into salts bysimply adding a stoichiometric amount of any selected acid and removingany water present by refluxing with benzene or the like. In fact, theselection of the solvent employed may depend in part whether or not theproduct at the completion of the reaction is to be converted into a saltform.

In the next succeeding paragraph it is pointed out that frequently it isconvenient to eliminate all solvent, using a temperature of not over 150C. and employing vacuum, if required. This applies, of course, only tothose circumstances where it is desirable or necessary to remove thesolvent. Petroleum solvents, aromatic solvents, etc., can be used. Theselection of solvent, such as benzene, xylene, or the like, dependsprimarily on cost, i, e., the use of the most economical solvent andalso on three other factors, two of which have been previouslymentioned; (a) is the solvent to remain in the reaction mass withoutremoval? (b) is the reaction mass to be subjected to further reaction inwhich the solvent, for instance, an alcohol, either low boiling or highboiling, might interfere as in the case of oxyalkylation? and the thirdfactor is this, (c) is an effort to be made to purify the reaction massby the usual procedure as, for example, a water-wash to remove thewater-soluble unreacted formaldehyde, if any, or a water-wash to removeany unreacted low molal soluble amine, if employed and present afterreaction? Such procedures are well known and, needless to say, certainsolvents are more suitable than others. Everything else being equal, wehave found xylene the most satisfactory solvent.

We have found no particular advantage in using a low temperature in theearly stage of the reaction because, and for reasons explained, this isnot necessary although it does apply in some other procedures that, in ageneral way, bear some similarity to the present procedure. There is noobjection, of course, to giving the reaction an opportunity to proceedas far as it will at some low temperature, for instance, 30 to 40 C. butultimately one must employ the higher temperature in order to obtainproducts of the kind herein described. If a lower temperature reactionis used initially the period is not critical, in fact, it may beanything from a few hours up to 24 hours. necessary or even desirable tohold the low temperature stage for more than 24 hours. In fact, we arenot convinced there is any advantage in holding it at this stage formore than 3 or 4 hours at the most. This, again, is

a matter of convenience largely for one reason. In heating and stirringthe reaction mass there is a tendency for formaldehyde to be lost. Thus,if the reaction can be conducted at a lower temperature so as to use uppart of the formaldehyde at such lower temperature, then the amount ofunreacted formaldehyde is decreased subsequently and makes it easier toprevent any loss. Here, again, this lower temperature is not necessaryby virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products ofreaction are mutually soluble, then agitation is required only to theextent that it helps cooling or helps distribution of the incomingformaldehyde. This mutual solubility is not necessary as previouslypointed out but may be convenient under certain circumstances. On theother hand, if the products are not mutually soluble then agitationshould be more vigorous for the reason that reaction probably takesplace principally at the interfaces and the more vigorous the agitationthe more interfacial area. -The general procedure employed is invariablythe same when adding the resin We have not found any case where it was iand the selected solvent, such as benzene or xylene. Refluxing should belong enough to insure that the resin added, preferably in a powderedform, is completely soluble. However, if the resin is prepared as suchit may be added in solution form, just as preparation is described inaforementioned U. S. Patent 2,499,368. After the resin is in completesolution the amine is added and stirred. Depending on the amineselected, it may or may not be soluble in the resin solution. If it isnot soluble in the resin solution it may be soluble in the aqueousformaldehyde solution. If so, the resin then will dissolve in theformaldehyde solution as added, and if not, it is even possible that theinitial reaction mass could be a threephase system instead of atwo-phase system although this would be extremely unusual. Thissolution, or mechanical mixture, if not completely soluble is cooled toat least the reaction temperature or somewhat below, for example 35 C.or slightly lower, provided this initial low temperature stage isemployed. The formaldehyde is then added in a suitable form. For reasonspointed out we prefer to use a solution and whether to use a commercial37% concentration is simply a matter of choice. In large scalemanufacturing there may be some advantage in using a 30% solution offormaldehyde but apparently this is not true on a small laboratory scaleor pilot plant scale. 30% formaldehyde may tend to decrease anyformaldehyde loss or make it easier to control unreacted formaldehydeloss.

Returning again to the preferred method of reaction and particularlyfrom the standpoint of laboratory procedure employing a glass resin pot,when the reaction has proceeded as far as one can reasonably expect at alow temperature; for instance, after holding the reaction mass with orwithout stirring, depending on whether or not it is homogeneous, at 30or 40 C. for 4 or 5 hours, or at the most, up to 10-24 hours, we thencomplete the reaction by raising the temperature up to 150 C., orthereabouts as required. The initial low temperature procedure can beeliminated or reduced to merely the shortest period of time which avoidsloss of amine or formaldehyde. At a higher temperature we use aphase-separating trap and subject the mixture to reflux condensation,until the water of reaction and the water of solution of theformaldehyde is eliminated. We then permit the temperature to rise tosomewhere about C., and generally slightly above 100 C., and below C.,by eliminating the solvent or part of the solvent so the reaction massstays within this predetermined range. This period of heating andrefluxing, after the water is eliminated, is continued until thereaction mass is homogeneous and then for one to three hours longer, Theremoval of the solvents is conducted in a conventional manner in thesame way as the removal of solvents in resin manufacture as described inaforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we haveinvariably employed approximately one mole of the resin based on themolecular weight of the resin molecule, 2 moles of the secondary amineand 2 moles of formaldehyde. In some instances we have added a trace ofcaustic as an added catalyst but have found no particular advantage inthis. In other cases we have used a slight excess of formaldehyde and,again, have not found any particular advantage in this. In other caseswe have used a slight excess of amine and, again, have not found anyparticular advantage in so doing. Whenever feasible we have checked thecompleteness of re: action, molecular weight, and particularly in someinstances have checked whether or not the end-product showedsurface-activity, particularly in a dilute acetic acid solution. Thenitrogen content after removal of unreacted amine, if any is present, isanother index.

In light of what has been said previously, little more need be said asto the actual procedure employed for the preparation of the hereindescribed condensation higher.

23 products. The following example will serve by way of illustration:

Example 1b held at a fairly low temperature (30 to 40 C.) for a periodof several hours. Then refluxing was employed until the odor offormaldehyde disappeared. After the odor of formaldehyde disappeared thephase-separating trap was employed to separate out all the water, boththe solution and condensation. After all the water had been separatedenough xylene was taken out to have the final product reflux for severalhours somewhere in the range of 145 to 150 C., or thereabouts. Usuallythe mixture yielded a clear solution by the time the bulk of the water,or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24examples in Table IV.

TABLE IV Strength of Reac- Reac- Max. Ex. Resin Amt., Amine used andamount formalde- Solvent used tlou, tion distill. No. used g'rs. hydesoln. and amt. 0. time, temp,

and amt. hrs. C.

882 Diethylamine, 146 grams 37%, 162 g Xylene, 882 g -25 30 150 480Diethylarnine, 73 grams 37%, 81 g Xylene, 480 g 22-30 24 152 633 o. 30%,100 g Xylene, 633 g 21-24 38 147 441 Dlbutylamlne, 129 grams 37%, 81 gXylene, 441 g- -37 32 149 480 do do Xylene, 480 g. 20-24 35 149 633 dodo Xylene, 633 18-23 24 150 882 Morpholine, 174 grams 37%, 162 g Xylene,882 g. 20-26 35 145 480 Morpholine, 87 grams 37%, 81 g Xylene, 480 g19-27 24 156 633 ...do o Xylene, 633 g." 20-23 24 147 473 Dioctylamine(di-Z-ethylhexyl 100 g Xylene, 473 g 20-21 38 148 665 do 37%, 81;;Xylene, (365 g". 20-26 24 150 441 (GzH5OC2H4OC OZNH, 250 gram 30%, 100 gXylene, 441 g- 20-22 31 147 480 (CzH5OO H4OGzHmNH, 250 grams. do Xylene,480 g.-. 20-24 36 148 595 (OZH5OCZH4OC2H4)ZNH, 250 grams 37%, 81 gXylene, 595 g 23-28 25 145 480 (OAHQOCHQCH(OH3)O(CH3)OHCH2)2NH, 361grams do Xylene, 480 g.-. 20-24 24 150 511 (041190013 611CH3)O(CH3)OHCH2)2NH, 361 grams 30%, 100 g- Xylene, 511 g... 20-22 25 146498 (CHaOCH2OHz CHzOHOCHzCHmNH, 309 grains" 37%, 81 g Xylene, 498 g--.20-25 24 140 542 (C1130CHZGHZOOHzGHgOOHzCHzhNH, 309 grams. .d Xylene,542 g... 28-38 30 142 547 (CHQOCHZCHQOOH2OH2OOH2CH2)2NH, 309 grams. .doXylene, 547 g--. 25-30 26 148 441 (CHQOCH2GH1CH2CH2CH3CHZ 2NH, 245 gramsdo- Xylene, 441 g. 20-22 28 143 595 (C1330 CH GHzCHzCHzCHgCHz)zNH, 245grams 30%, 100 Xylene, 595 g. 18-20 25 140 24b 27a 391(OHSOGHQCHECHZGHQGHZGHQZNH, 98 grams. 30%, 50 g... Xylene, 391 g 19-2224 145 nuclei. The resin so obtained in a neutral state had a PART 7light amber color.

882 grams of the resin identified as 2a, preceding, were powdered andmixed with an equal weight of xylene, i. e., 882 grams. The mixture wasrefluxed until solution was complete. It was then adjusted toapproximately 30 C. to C., and 146 grams of diethylamine added. Themixture was stirred vigorously and formaldehyde added slowly. Theformaldehyde was used as a 37%. solution and 162 grams were employed,which were added in about 2 /2 hours. The mixture was stirred vigorouslyand kept within a temperature range of 30 to C. for about 20 hours. Atthe end of this period of time it was refluxed, using a phase-separatingtrap and a small amount of aqueous distillate withdrawn from time totime, and the presence of unreacted formaldehyde noted. Any unreactedformaldehyde seemed to disappear within 2 to 3 hours after refluxing wasstarted. As soon as the odor of formaldehyde was no longer detectiblethe phase-separating trap was set so as to eliminate all water ofsolution and reaction. After the water was eliminated part of the xylenewas removed until the temperature reached approximately 145 C., orslightly The mass was kept at this higher temperature for about 4 hoursand reaction stopped. During this time any additional water, which wasprobably water of reaction which had formed, was eliminated by means ofthe trap. The residual xylene was permitted to stay in the cogenericmixture. A small amount of the sample was heated on a water bath toremove the excess xylene and the residual material was dark red in colorand had the consistency of a sticky fluid or tacky resin. The overalltime for the reaction was about 30 hours. Time can be reduced by cuttinglow temperature period to approximately 3 to 6 hours.

Note that in Table IV following there are a'large number of addedexamples illustrating the same procedure. In each case the initialmixture was stirred and The products obtained as herein described byreactions involving amine condensates and diglycidyl ethers or theequivalent are valuable for use as such. This is pointed out in detailelsewhere. However, in many instances the derivatives obtained byoxyalkylation are even more valuable and from such standpoint the hereindescribed products may be considered as valuable intermediates.Subsequent oxyalkylation involves the use of ethylene oxide, propyleneoxide, butylene oxide, glycide, etc. Such oxyalkylating agents aremonoepoxides as differentiated from polyepoxides.

It becomes apparent that if the product obtained is to be treatedsubsequently with a monoepoxide which may require a pressure vessel asinthe case of ethylene oxide, it is convenient to use the same reactionvessel in both instances. In other words, the 2 moles of theaminemodified phenol-aldehyde resin condensate would be reacted with apolyepoxide and then subsequently with a monoep'oxide. In any event, ifdesired the polyepoxide reaction can be conducted in an ordinaryreaction vessel, such as the usual glass laboratory equipment. This isparticularly true of the kind used for resin manufacture as described ina number of patents, as for example, U. S. Patent No. 2,499,365.

Cognizanc'e should be taken of one particular feature in connection withthe reaction involving the polyepoxide and that is this; theamine-modified phenol-aldehyde resin condensate is invariably basic andthus one need not add the usual catalysts which are used to promote suchreactions. Generally speaking, the reaction will proceed at asatisfactory rate under suitable conditions without any catalyst at all.

Employing polyepoxides in combination with a nonbasic reactant the usualcatalysts include alkaline materials such as caustic soda, causticpotash, sodium methylate, etc. Other catalysts may be acidic in natureand are 25 of the kind characterized by iron and tin chloride.Furthermore, insoluble catalysts such as clays or specially preparedmineral catalysts have been used. If for any reason the reaction did notproceed rapidly enough with the table, the examples are characterized bythe fact that no alkaline catalyst was added. The reason is, of course,that the condensate as such is strongly basic. If desired, a smallamount of an alkaline catalyst could be added,

diglycidyl ether or other analogous reactant, then a small such asfinely powdered caustic soda, sodium methylate, amount of finely dividedcaustic soda or sodium methylate etc. If such alkaline catalyst is addedit may speed up could be employed as a catalyst. The amount generallythe reaction but it also may cause an undesirable reacemployed would be1% or 2%. tion, such as the polymerization of a diepoxide.

It goes without saying that the reaction can take place In any event,105 grams of the condensate dissolved in an inert solvent, i. e., onethat is not oxyalkylationin 105 grams of xylene were stirred and heatedto 100 C., susceptible. Generally speaking, this is most convenient- 17grams of the diepoxide previously identified as 3A and ly an aromaticsolvent such as xylene or a higher boiling dissolved in an equal weightof xylene were added dropcoal tar solvent, or else a similar highboiling aromatic wise. An initial addition of the xylene solutioncarried solvent obtained from petroleum. One can employ an thetemperature to about 106 C. The remainder of oxygenated solvent such asthe diethylether of ethylene diepoxide was added during approximately anhours time. glycol, or the diethylether of propylene glycol, or similarDuring this period of time the temperature rose to about ethers, eitheralone or in combination with a hydrocarbon 125 C. The product wasallowed to reflux at a temperasolvent. The selection of the solventdepends in part on ture of about 130 C. using a phase-separating trap. Athe subsequent use of the derivatives or reaction products. small amountof xylene was removed by means of a If the reaction products are to berendered solvent-free 20 phase-separating trap so the refluxingtemperature rose and it is necessary that the solvent be readily removedgradually to about a maximum of 180 C. The mixture as, for example, bythe use of vacuum distillation, thus was then refluxed at 180 forapproximately 4 hours until xylene or an aromatic petroleum will serve.If the prodthe reaction stopped and the xylene which had been reuct isgoing to be subjected to oxyalkylation subsequently, moved during thereflux period was returned to the mixthen the solvent should be onewhich is not oxyalkylationture. A small amount of material was withdrawnand susceptible. It is easy enough to select a suitable solvent thexylene evaporated on the hot plate in order to examif required in anyinstance but, everything else being equal, ine the physical properties.The material was a dark the solvent chosen should be the most economicalone. red viscous semi-solid. It was insoluble in water, it was Example10 insoluble in 5% gluconic acid, and it was soluble in xylene, andparticularly in a mixture of 80% xylene and The product was obtained byreaction between the 20% methanol. However, if the material wasdissolved diepoxide previously designated as diepoxide 3A, and in anoxygenated solvent and then shaken with 5% condensate 1b. Condensate lbwas obtained from resin gluconic acid it showed a definite tendency todisperse, 2a. Resin 2a was obtained from tertiary'butylphenol andsuspend, or form a sol, and particularly in a xylene-methformaldehyde.Condensate lb employed as reactants anol mixed solvent as previouslydescribed, with or withresin 2a and diethylamine. The amount of resinemout the further addition of alittle acetone. ployed was 882 grams; theamount of diethylamine em- The procedure employed of course is simple inlight ployed was 146 grams; the amount of 37% formaldehyde of what hasbeen said previously and in eifect is a employed was 162 grams, and theamount of solvent emprocedure similar to that employed in the use ofglycide ployed was 882 grams. All this has been described -pre- 40 ormethylglycide as oxyalkylating agents. See, for examviously. ple, Part 1of U. S. Patent No. 2,602,062, dated July 1,

The solution of the condensate in xylene was adjusted 1952, to DeGroote. I to a solution. In this particular instance, and in Variousexamples obtained in substantially the same practically all the otherswhich appear in a subsequent manner are enumerated in the followingtables:

TABLE V Con- Time Ex. den- Amt., Diep- Amt, Xylene, Molar oi reac- Max.No. sate grs. oxide grs. grs. ratio tion, temp, Color and physical stateused used hrs. 0.

3A 17 122 2:1 5 180 Dark viscous semi-solid. 124 3A 17 141 2:1 6 190 Do.108 3A 17 125 2:1 5 132 Do. 3A 17 133 2:1 6 190 Do. 3A 17 123 21 s D0.159 3A 17 176 2:1 3 192 Dark solid. 141 3A 17 158 2:1 6.5 Dark viscoussemi-solid. 177 3A 17 194 2:1 8 188 Dark solid. 164 3A 17 181 2:1 7 190Dark viscous semi-solid. 173 3A 17 190 2:1 8 190 Dark solid.

Solubility in regard to all these compounds was substantially similar tothat which was described in Example 10 TABLE VI Con- Time Ex. den- Amt,Diep- Amt., Xylene, Molar of reac- Max. No. sate grs. oxide grs. grs.ratio tion, temp., Color and physical state used used I hrs. C.

105 B1 27. 5 132. 5 2:1 6 182 Dark viscous semi-solid. 124 B1 27. 5 151.5 2:1 6 190 D0. 108 B1 27. 5 135. 5 2:1 6 185 D0. 116 B1 27. 5 1'13. 52:1 6 190 D0. 120 B1 27. 5 197. 5 2:1 7 D0. 159 B1 27. 5 186. 5 2: 1 8190 Dark solid. 141 B1 27. 5 168. 5 2:1 7 194 Dark viscous semi-solid.177 B1 1 27. 5 204. 5 2:1 8 190 Dark solid. 164 B1 I 27. 5 191. 5 2:1 8188 Dark viscous semi-solid. 173 B1 27. 5 200. 5 2:1 8 200 Dark solid.

Sblubilityjn regard to all these compounds was substantially similar tothat whieliwas described in Example 1c.

TABLE VII Probable Resin con- Probable Amt. of Amt. of number of Ex. N0.densate mol. wt. of product, solvent, hydroxvls used reaction grs. grs.per moleproduet cule 2, 500 2, 500 l, 250 ll 2, 660 2, 675 l, 345 11 2,740 2, 705 1, 11 3, 520 3, 505 1, 765 11 TABLE VIII I Probable Rosincon- Probable Amt. of Amt, of number of Ex. N0. densate mol. Wt. ofproduct, solvent, hydroxyls used reaction grs. grs. per moleproduct culo2, 650 2, 670 1, 34s 11 3,030 3,045 1.530 ll. 2,710 2,710 1,355 11 2,8702,880 1,445 11 2, 950 2,955 l, 480 11 3, 730 3, 730 1, 865 ll 3, 350 3,365 1, 690 11. 4, 090 4, 080 2, 035 n 3, 830 3, 830 1, 915 12 4, 010 4,025 2, 020 12 At times we have found a tendency for an insoluble mass toform or at least to obtain incipient cross-linking or gelling even whenthe inolal ratio is in the order of 2 moles of resin to one ofdiepoxidc. We have found this can be avoided by any one of the followingprocedures or their equivalent. Dilute the resin or the diepoxide, orboth, with an inert solvent, such as xylene or the like. In someinstances an oxygenated solvent, such as the diethyl ether of:ethyleneglycol maybe employed. Another procedure which is helpful is toreduce the amount of catalyst used, or reduce the temperature ofreaction by adding a small amount of initially lower boiling solventsuch as benzene, or use benzene entirely. Also, we have found itdesirable at times to use slightly less than apparently the theoreticalamount of diepoxide, for instance 90% to 95% instead of 100%. The reasonfor this fact may reside in the possibility that the ,molecular weightdimensions on either the resin molecule or the diepoxide molecule mayactually vary from the true molecular weight by several percent.

Previously the condensate has been depicted in a simplified form which,for convenience, may be shown thus:

(Amine) CH2(Resin CHz(Amine) Following such simplification the reactionproduct with a polyepoxide and particularly a diepoxide, would beindicated thus:

[(Amine) CH2 (Rosin) CH; (Aminefl [D. G. E.]

[(Amine) CH (Rosin) CH (Arnine)] in which D. G. E. represents adiglycidyl ether as specified. If the amine happened to have more thanone reactive hydrogen, as in the case of a hydroxylated amine orpolyamine, having a multiplicity of secondary amino with a polyepoxide.

23 groups it is obvious thatother side reactions could take place asindicated by the following formulas:

[(Amino) CH2 (Aminefl [D. G. E.]

[(Amine) CH (Aminefl [(Resin) CH (Resin)] [D. G. E.]

[(Resin) CH (Resin)] [(Amine) CH2 (Aminefl Rcsin)] All the aboveindicates the complexity of the reaction product obtained after treatingthe amine-modifiedresin condensate with a polyepoxide and particularlydiepoxide as herein described.

PART 8 ally, for purpose of convenience, it is most desirable toconductthe previous reaction, i. e., the one involving the polyepoxide, inequipment such that subsequent reaction with monoepoxides may followwithout interruption. In the oxyalkylations carried out to producecompositions used in accordance with the present application,conventional equipment,'i. e., a stainless steel autoclave suitablyequipped, and conventional oxyalkylation conditions were used.

The amount of'rnonoepoxides employed may be as high as 50 parts ofmonoepoxide for one part of the polyepoxide treated amine-modifiedphenol-aldehyde condensation product.

Example 1 E The polyepoxide-derived oxyalkylation susceptible compoundemployed is the one previously designated and described as Example lD.Polyepoxide-derived condensate ID was obtained, in turn, from condensatelb and diepoxide B1. Reference to Table lV shows the composition ofcondensate lb. Table IV shows it was obtained from resin 2a,diethylamine and formaldehyde. Table III shows that resin 2a wasobtained from tertiary butylphenol and formaldehyde.

For purpose of convenience, reference herein and in the tables to theoxyalkylation-susceptible compound will be abbreviated in the tableheading as 05C; reference is to the solvent-free material since, forconvenience, the amount of solvent is noted in a second column.Actually, part of the solvent may have been present and in practicallyevery case was present in either the resinification process or thecondensation process, or in treatment In any event, the amount ofsolvent present at the time of treatment wtih a monoepcxide is indicatedas a separate item. To be consistent, of course, theoxyalkylation-susceptible compound abbreviated as OSC is indicated on asolvent-free basis.

13.25 pounds of the polyepoxide-derived condensate were mixed with 13.45pounds of solvent (xylene in this series) along with one pound of finelypowdered caustic soda as a catalyst. This reaction mixture was treated29 with 13.25 pounds of ethylene oxide. At the end of the reactionperiod the molal ratio of oxide to initial compound was approximateIy60.25, and the theoretical molecular weight was approximately 5300.

Adjustment was made in the autoclave to operate at a temperature of 125to 130 C., and at a pressure of to pounds per square inch.

The time regulator was set so as to inject the ethylene oxide inapproximately one-half hour and then continued stirring for one-halfhour longer simply as a precaution to insure complete reaction. Thereaction went readily and, as a matter of fact,'the ethylene oxide couldhave been injected in probably 15 minutes instead of a halfhour and thesubsequent time allowed to insure completion of reaction may have beenentirely unnecessary. The speed of reaction, particularly at the lowpressure, undoubtedly was due in a large measure to the excellentagitation and also to the comparatively high concentration 'of catalyst.The amount of ethylene oxide introduced, as previously noted, was 13.25pounds.

A comparatively small sample, less than 50 grams, was withdrawn merelyfor examination as far as solubility or emulsifying power was concerned,and also for the purpose of making some tests on various oil fieldemulsions. The amount withdrawn was so small that no cognizance of thisfact is included in the data or subsequent data, or in data reported intabular form in subsequent Tables IX, X and XI.

The size of the autoclave employed was 35 gallons. In innumerableoxyalkylations we have withdrawn a substantial portion at the end ofeach step and continued oxyalkylation on a partial residual sample. Thiswas not the case in this particular series. Certain examples wereduplicated as hereinafter noted and subjected to oxyalkylation with adifferent oxide.

Example 2E This example simply illustrates further oxyalkylation ofExample 1E, preceding. The oxyalkylation-susceptible compound, to wit,Example 1D, is the same one as was used in Example 1E, preceding,because it is merely a continuation. In the subsequent tables, such asTable IX, the oxyalkylation-susceptible compound in the horizontal lineconcerned with Example 2E referes to oxyalkylationsusceptible compound,Example 1D. Actually, one could refer just as properly to Example 1E atthis stage. It is immaterial which designation is used so long as it isunderstood and such practice is used consistently throughout the tables.In any event, the amount of ethylene oxide is the same as before, towit, 13.25 pounds. This means the amount of oxide at the end was 26.5pounds. It is meant that the ratio of oxide to oxyalkylationsusceptiblecompound (molar basis) at the end was 120.5 to 1. The theoreticalmolecular weight was almost 8,000. There was no added solvent. In otherwords, it remained the same, that is, 13.45 pounds, and there was noadded catalyst. The entire procedure was substantially the same as inExample 1E, preceding.

In all succeeding examples the time and pressure were the same aspreviously, to wit, 125 to 130 C., and the pressure 10 to 15 pounds. Thetime element was onehalf hour, the same as before.

Example 3E The oxyethylation proceeded in the same manner as describedin Examples 1E and 2E. There was no added solvent and no added catalyst.The oxide added was 13.25 pounds. The total oxide at the end of theoxyalkylation procedure was 39.75 pounds. The molal ratio of oxide tocondensate was 180 to 1. The theoretical molecular weight wasapproximately 10,600. As previously noted, conditions in regard totemperature and pressure were the same as in Examples 1E and 2E. Thetime period also was the same, to wit, one-half hour.

30 Example 4E The oxyethylation was continued and the amount of oxideadded was the same as before, to wit, 13.25 pounds. The amount of oxideadded at the end of the reaction was 53 pounds. There was no addedsolvent and no added catalyst. Conditions as far as the temperature andpressure are concerned were the same as in previous examples. The timeperiod was slightly longer, to wit, 45 minutes. The reaction at thispoint showed modest, if any, tendency to slow up. The molal ratio ofoxide to oxyalkylation-susceptible compound was about 240 to l and thetheoretical molecular weight was 13,250.

Example 5E The oxyalkylation was continued with the introduction ofanother 13.25 pounds of oxide. No added solvent was introduced, andlikewise no added catalyst was introduced. The theoretical molecularweight at the end of the reaction was approximately 1 8,500. The molalratio of oxide to oxyalkylation-susceptible compound was 360 to 1. Thetime period was one hour.

Example 6E The same procedure was followed as in the previous exampleswithout addition of either more catalyst or more solvent. The amount ofoxide added was the same as before, to wit, 13.25 pounds. The timerequired to complete the reaction was one hour. At the end of thereaction the ratio of oxide to oxyalkylation-susceptible compound wasapproximately 480 to 1, and the theoretical molecular weight was about24,000.

The same procedure as described in the previous examples was employed inconnection with a number of the other condensations describedpreviously. All these data have been presented in tabular form in TablesIX through XIV, inclusive.

In substantially every case a 35-gallon autoclave was employed, althoughin some instances the initial oxyethylation was started in a 15-gallonautoclave and then transferred to a 25-gallon autoclave. This isimmaterial but happened to be a matter of convenience only. The solventused in all cases was xylene. The catalyst used was finely powderedcaustic soda.

Referring now to Tables IX, X and XI, it will be noted that compounds 1E through 18E were obtained by the use of ethylene oxide, whereasExamples 19E through 36E were obtained by the use of propylene oxide;and Examples 37E through 54E were obtained by the use of butylene oxide.

Referring now to Table X specifically, it will be noted that the seriesof examples beginning with IE were obtained, in turn, by use of bothethylene and propylene oxides, using ethylene first; in fact, usingExample 1E as the oxyalkylation-susceptible compound in the first sixexamples. This applies to series 1F through 18F.

Similarly, series 19F through 36F involve the use of both propyleneoxide and ethylene oxide in which the propylene oxide was used first, towit, 19F was prepared from 21E, a compound which was initially derivedby use of propylene oxide.

Similarly, Examples 37E through 54F involve the use of ethylene oxideand butylene oxide, the ethylene oxide being used first. Also, these twooxides Were used in the series 55F through 72F, but in this latterinstance the butylene oxide was used first and then the ethylene oxide.

Series 73F through F involve the use of propylene oxide and butyleneoxide, butylene oxide being used first and propylene oxide being usednext.

In series 16 through 18G the three oxides were used. It will be noted inExample 1G the initial compound was 78F; Example 78F, in turn, wasobtained from a "'31 compound in which butylene oxide was used initiallyand then propylene oxide. Thus, the oxide added in the series 16 through66 was by use of ethylene oxide as indicated in Table XI.

Referring to Table XI, in regard to Example 196 it will be noted againthat the three oxides were used and 196 was obtained from 59F. Example59F, in turn, was obtained by using butylene oxide first and thenethylene oxide. In Example 19G and subsequent examples, such as G, 21G,etc., propylene oxide was added.

Tables XII, XIII and XIV give the data in regard to the oxyalkylationprocedure as far as temperature and pressure are concerned and also givesome data as to solubility of the oxyalkylated derivative in water,xylene and kerosene.

Referring to Table IX in greater detail, the data are as follows: Thefirst column gives the example numbers, such as 1E, 2E, 3E, etc.; thesecond column give the oxyalkylation-susceptible compound employedwhich, as previously noted in the series l-E through 6B, is Example 1D,although it would be just as properto say that in the case of 2B theoxyalkylation-susceptible compound was 1E, and in the case of 3E theoxyalkylation-susceptible compound was 2E. Actually reference is to theparent derivative for the reason that the figure stands constant andprobably leads to a more convenient presentation. Thus, the third columnindicates the polyexpoxide-derived condensate previously referred to inthe text.

- The fourth column shows the amount of ethylene oxide in the mixtureprior to the particular oxyethylation step. In the case of Example 1Ethere is no oxide used but it appears, of course, in 2E, 3E and 4E, etc.

The fifth column can be ignored for the reason that it is concerned withpropylene oxide only, and the sixth column can be ignored for the reasonthat it is concerned with butylene oxide only.

The seventh column shows the catalyst which is invariably powderedcaustic soda. The quantity used is indicated.

The eighth column shows the amount of solvent which is xylene unlessotherwise stated.

The ninth column shows the amount of the oxyalkylation-susceptiblecompound which in this series is the polyepoxide-derived condensate.

The tenth column shows the amount of ethylene oxide in at the end of theparticular step.

Column eleven shows the same data for propylene oxide, and column twelvefor butylene oxide. For obvious reasons these can be ignored in theseries 1E through 18E.

Column thirteen shows the amount of the catalyst at the end of theoxyalkylation step, and column fourteen shows the amount of solvent atthe end of the oxyalkylatron step.

The fifteenth, sixteenth and seventeenth columns are concerned withmolal ratio of the individual oxides to the oxyalkylation-susceptiblecompound. Data appears only in column fifteen for the reason, previouslynoted, that no butylene or propylene oxide were used in the presentinstance.

The theoretical molecular weight appears at the end of the table whichis on the assumption, as previously noted, as to the probable molecularweight of the initial compound, and on the assumption that all oxideadded during the period combined. This is susceptible to limitationsthat have been pointed out elsewhere, particularly in the patentliterature.

Referring now to the second series of compounds in Table IX, to wit,Example 19E through 36E, the situation is the same except that it isobvious the oxyalkylating agent used was propylene oxide and notethylene oxide. Thus, the fourth column becomes a blank and the tenthcolumn becomes a blank and the fifteenth column be comes a blank, butcolumn five, which previously was a blank in Table IX now carries dataas to the amount of propylene-oxide present at the beginning of thereaction. Column eleven carries data as to the amount of propylene oxidepresent .at the end of the reaction, and column sixteen carries data asto the ratio of propylene oxide to the oxyalkylation-susceptiblecompound. In all other instances the various headings have the samesignificance as previously.

Similarly, referring to Examples 37E through 54E in Table IX, columnsfour and five are blanks, columns ten and eleven are blanks, and columnsfifteen and sixteen are blanks, but data appear in column six as tobutylene oxide present before the particular oxyalkylation step. Columntwelve gives the amount of butylene oxide present at the end of thestep, .and column seventeen gives the ratio of butylene oxide tooxylkylation-susceptible compound.

Table X is in essence the data presented in exactly the same way exceptthe two oxides appear, to wit, ethylene oxide and propylene oxide. Thismeans that there are only three columns in which data does not appear,all three being concerned with the use of butylene oxide. Furthermore,it shows which oxide was used first by the very fact that reference toExample 1F, in turn, refers to IE, and also shows that ethylene oxidewas present at the very first stage. Furthermore, for ease of comparisonand also to be consistent, the data under Molal Ratio in regard toethylene oxide and propylene oxide goes back to the originaldiepoxide-derived condensate 1D. This is obvious, of course, because thefigures 60.25 and 23.3 coincide with the figures for'lE derived from ID,as shown in Taxle IX.

In Table X the same situation is involved except, of course, propyleneoxide is used first and this, again, is perfectly apparent. Threecolumns only are blank, to wit, the three referring to butylene oxide.The same situation applies in Examples such as 37F and subsequentexamples where the two oxides used are ethylene oxide and butyleneoxide, and the table makes it plain that ethylene oxide was used first.Inversely, Example 55F and subsequent examplesshow the use of the sametwo oxides but with butylene oxide being used first as shown on thetable. I

Example 73F and subsequent examples relate to the use of propyleneoxideand butylene oxide. Examples be ginning with 16, Table XI,particularly 2G, 36, etc., show the use of all three oxides so there areno blanks as in the first step of each stage where one oxide is missing.It is not believed any further explanation need be olfered in regard toTable XI.

As previously pointed out certain initial runs using one oxide only, orin some instances two oxides, had to be duplicated when used asintermediates subsequently for further reaction. It would be confusingto refer in too much detail in these various tables for the reason thatall pertinent data appear and the tables are essentially selfexplanatory.

Reference to solvent and amount of alkali at any point takes intoconsideration the solvent from the previous step and the alkali leftfrom this step. As previously pointed out, Tables XII, XIII and XIV giveoperating data inconnection with the entire series, comparable to whathas been said in regard to Examples 1E through 6E.

The products resulting from these procedures may contain modest amounts,or have small amounts, of the solvents as indicated by the figures inthe tables. If desired, the solvent maybe removed by distillation, andparticularly vacuum distillation. Such distillation also may removetraces or small amounts of uncombined oxide, if present and volatileunder the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide incombination one need not first use one oxide and then the other, but onecan mix the two oxides and thus obtain what may be termed an indilferentoxyalkylation,

33 i. e., no attempt to selectively add one and then the other, or anyother variant.

Needless to say, one could start with ethylene oxide and then usepropylene oxide, and then go back to ethylene oxide; or, inversely,start with propylene oxide, then use ethylene oxide, and then go back topropylene oxide; or, one could use a combination in which butylene oxideis used along with either one of the two oxides just men tioned, or acombination of both of them.

The same would be true in regard to a mixture of ethylene oxide andbutylene oxide, or butylene oxide and propylene oxide.

The colors of the products usually vary from a reddish amber tint to adefinitely red, amber and to a straw or light straw color. The reason isprimarily that no effort is made to obtain colorless resins initiallyand the resins themselves may be yellow, amber, or even dark amber.Condensation of a nitrogenous product invariably yields a darker productthan the original resin and usually has a reddish color. The solventemployed, if xylene, adds nothing to the color but one may use a darkercolored 5 or straw color with a reddish tint.

be decolorized by the use of clays, bleaching chars, etc.

aromatic petroleum solvent. Oxyalkylation generally tends to yieldlighter colored products and the more oxide employed the lighter thecolor the product. Products can be prepared in which the final color isa lighter amber Such products can As far as use in demulsification isconcerned, or some other industrial uses, there is no justification forthe cost of bleaching the product.

10 Generally speaking, the amount of alkaline catalystpresent iscomparatively small and it need not be re moved. Since the products perse are alkaline due tothe presence of a basic nitrogen, the removal ofthe alkaline catalyst is somewhat more difficult than ordinarily is the15 case for the reason that if one adds hydrochloric acid,

for example, to neutralize the alkalinity one may part-ially neutralizethe basic nitrogen radical also. The preferred procedure is to ignorethe presence of the alkali unless it is objectionable or else add astoichiometric 20 amount of concentrated hydrochloric acid equal to thecaustic soda present.

TABLE IX Composition before Composition at end E Oxides Oxides Molalratio x. No. 080, Cata- Sol- Cata- Sol- Theo. ex. 080, lyst, vent, S0,lyst, vent, gg P gf g f moi. No. 8. EtO, IPrO, BuO, lbs. lbs. lbs. EtO,PrO, BuO, lbs. lbs. alga. alkyl g wt.

lbs. lbs. lbs. lbs. lbs. lbs. n gmmpt susceph cmpd. cmpd. cmpd. 1E... 1D13.25 1. 0 13. 45 13. 25 13. 25 1.0 13. 45 60. 25 2 1D 13.25 13.25 1. 013.45 13. 25 .26. 50 1.0 13. 45 120. 3E 1D 13.25 26. 50 1. 0 13. 45 13.25 39. 75 1.0 13.45 180. 75 4E... 1D 13. 25 39. 75 1. 0 13.45 13.25 .53.0 1.0 13.45 241.0 5E... 1D 13.25 53. 0 1. 0 13. 45 13.25 v79. 5 1.013.45 361. 5 6E... 1D 13.25 79. 5 1. 0 13. 45 13.25 106.0 1. 0 13.45482.0 7E 2D 15. 15 1. 5 15.30 15. 15 .15. 0 1. 5 15.30 68. 2 8E... 2D15. 15 15.0 1. 5 15.30 15. 15 20. 0 1. 5 15.30 136. 4 9E. 2D 15. 1530.0 1. 5 15.30 15.15 45. 0 1. 5 15.30 204. 6 10 2D 15.15 45.0 1. 5 15.80 15. 60.0 1. 5 15.30 272. 8 11E-- 2D 15. 15 60. 0 1. 5 15.30 15. 1590. 0 1. 5 15.30 40. 92 12E.. 2D 15. 15 90.0 1. 5 15.30 15. 15 120. 0 1.5 15.30 545. 6 13E 3D 13. 55 1.0 13.55 13.55 13. 5 1.0 13.55 61. 41415.. 3D 13.55 13. 5 1.0 13. 55 13.55 27. 0 1.0 13.55 122. 8 1513.. 3D13.55 27. 0 1. 0 13. 55 13. 55 40. 5 1.0 13. 55 184. 2 16E... 3D 13. 5540. 5 1. 0 13. 55 13.55 .54. 0 1.0 13. 55 245. 6 1751.. 3D 13. 55 54.0 1. 0 13.55 13. 55 81. 0 1. 0 13.55 368.4 18E- 3D 13.55 81. 0 1.0 13.55 13.55 108.0 1. 0 13 55 491. 2 24, 330 19E.. 1D 13. 25 1. 0 13. 4513.25 1.0 13. 45 46. 4 5, 300 20E. 1D 13. 13. 25 1. 0 13. 45 13.25 1. 013.45 1 92.8 7, 950 21E. 1 13. 25 26. 50 1. 0 13. 45 13. 25 1. O 13.45139. 2 10. 600 22E 1D 13.25 39. 75 1. 0 13.45 13.25 1. 0 13.45 185. 613. 250 2315.. 1D 13.25 53. 0 1.0 13.45 13.25 1. 0 13. 45 278. 4 18, 5502415.. 1D- 13. 25 79. 5 1. 0 13. 45 13. 25 1. 0 13.45 371. 2 ,850 25E 2D15. 15 1. 5 15.30 15. 15 1. 5 15. 51. 7 6,030 26E. 2D 15.15 15. 0 1. 515.30 15. 15 1. 5 15.30 103. 4 9,030 2715.. 2D 15. 15 30. 0 1. 5 15.3015.15 1. 5 15.30 155. 1 12,030 2815.. 2D 15.15 45.0 1. 5 15.30 15.15 1.5 15.30 205. 8 .030 29E... 2D 15. 15 60. 0 1. 5 15. 30 15. 15 1. 5 15.30 310.2 21, 030 3013* 2D 15. 15 90.0 1. 5 15. 30 15.15 1. 5 15. 30 413.6 27,030 311:... 3 13.55 1. 0 13. 55 13.55 1.0 13. 55 46. 5 5, 4103213.. 3 13. 55 13. 5 1. 0 13. 55 13. 55 1.0 13.55 93. 0 8,110 33E 3D,-"13.55 27. 0 1.0 13.55 13. 55 1. 0 13.55 139. 5 10. 810 3413.. 3 13.5540. 5 1. 0 13. 55 13.55 1.0 13.55 186. 0 13, 510 35E 3D 13.55 54.0 1. 013. 55 13.55 1.0 13. 55 279.0 18, 920 3515.. 3D 13. 55 S1. 0 1. 0 18. 55.13. 55 1.0 13. 55 372.0 24. 330 3715.. 1 13. 25 1. 0 13.45 13.25 6. 751.0 13.45 5 4, 000 3815.. 1 13.25 1. 0 13. 45 13. 25 13.50 1.0 13.45 37.50 5, 350 39E 1D 13. 25 1. 0 13.45 13.25 20.25 1.0 13.45 56.25 6, 70040E 1D 13. 25 l. 0 13. 13. 25 27.0 1.0 13.45 75.0 8, 050 41E 1 13. 25 1.0 13. 45 13.25 33. 75 1.0 13.45 112.5 9, 400 42E. 1D.. 13. 25 1.0 13. 4513.25 54. 0 1. 0 13.45 150.0 13, 450, 43E 2D 15. 15 1. 0 15. 30 15.15 7.5 1. 0 15.30 20.8 4, 530 44E... 2 15. 15 7. 5 1. 0 15.30 15. 15 15.0 1.015.30 41. 6 6, 030 45E 2 15. 15 15. 0 1.0 15.30 15. 15 22. 5 1.0 15.3062. 4 7, 530 46E. 2D 15.15 22.5 1. 0 15.30 15.15 37. 5 1.0 15.30 104.010, 530 47E 2D 15.15 37. 5 1. 0 15. 30 15. 15 52. 5 1. 0 15. 30 146.0530 48E 2 15. 15 52.5 1.0 15.30 15. 15 67. 5 1.0 15.30 187. 2 16, 53049E 3D- 13.55 1.0 13. 55 13. 55 6. 75 1. 0 13.55 18. 7 3, 955 5013.. 3D13.55 6. 75 1.0 13. 55 13. 55 13. 50 1. 0 13.55 37. 4 5, 300 51E 3 13.5513.50 1. 0 13. 13.55 20.25 1.0 13.55 56. 1 6, 645 52E. 3 13. 55 20.251.0 13. 55 13. 55 27.0 1.0 13.55 74. 8 8, 090. 53E 3 13.55 27. 0 1. 013. 55 13.55 40. 5 1.0 13.55 112. 2 10, 780 54E 3 13. 55 40. 5 1. 0 13.55 13. 55 54.0 1. 0 13. 55 149. 6 13, 470

Theo.

ox alkyl.

cmpd.

7777774 4 4A 44444444-5555556666fl-699999 333333000o0077777777777744444444444 11.1111 111111111111 Molel ratio 0 alkyl.

EtOto PrO to BuO to mol.

alkyl.

cmpd. cmpd.

suscept. suscept. suscept.

mmmmnmu m mmmwemnnnmm 11 3 11 111111111111111222222 Solvent,

555555 00000555.055555555000000555555 44444.4 3333355555544444 555555 $333 ?3555555omqmaqmflwqmqwnmqwnmomfim5ixm5ixmaomnmnm39m111111111111111111111111111111111111 Catalyst, lbs.

555555555555555555555555555555555555LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL Composition at end 7 7777777777777444 44 BBBBBB3WWW332222222222ZWmMflWflHMERoG 55 Oxides PrO, B110,

EtO,

A 8 7 Q 7 L5 2J &9 2 L0 7 7 7 7 7 7 2 222220000 B124 1123B2342222222222226666W BBBBBBlllIlIBBBBBBHBBBBBllfilllBBBBBB Solvent,

lbs. 7

Catalyst,

BuO, lbs.

lbs.

Oxides EtO, PrO,

Composltlon before M BBBBBHMHMwEHBBBBBBBBBBBBHMMHHHBBBEBEIIIIII:IIIIIII:In": Sum o mmmnmmssmmsm553533535555 .z. z meeeeeeeeeeeeeeeeeefineaeae EN lwwmwwmmmmnmmnmmumwmmmnmfiwnwwmuafiwKerosene Soluble. Insoluble.

Disperslble.

Soluble. Do. Do. Insoluble.

Soluble.

Dlsperslble.

Soluble. Do. Insoluble.

Do. Disperslble.

Soluble. Do. Do.

Solubillty Xylene Water TABLE XII Time, hrs.

Max.

pres.,

Max. temp., C.

Ex. No.

EXAMPLE XIII h Time hrs.

Solubility Kerosene rw wwwwwwwmmwwow-wzen X XX XX k Do. Soluble. D0.Dlspersible. Insoluble.

Dispersible':

In soluble Soluble.

Dlspersible.

Insoluble.

Do. Do;

Do. Soluble;

DU: 7 Insoluble.

Insoluble.

Disnetslble;

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPECHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER,SAID DEMULSIFIER BEING OBTAINED BY A 3-STEP MANUFACTURING METHODINVOLVING (1) CONDENSATION: (2) OXYALKYLATION WITH A POLYEPOSCIDE; AND(3) OXYALKYLATION WITH A MONOEPOSCIDE; AND FIRST MANUFACTURING PROCESSBEING A STEP OF (A) CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE,FUSIBLE, NON-OXYGENATED ORANGIC SOLVENT-SOLUBLE, WATER-INSOLUBLE,LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHTCORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESINMOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TOMETHYLOL-FORMING REACTIVITY: SAID RESIN BEING DERIVED BY REACTIONBETWEEN A DIFUNCTIONAL MONOHYDIC PHENOL AND A ALDEHYDE HAVING NOT OVER 8CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED INTHE SUBSTANTIAL ABSENCE OF TRI-FUNCTIONAL PHENOLS; SAID PHENOL BEING OFTHE FORMULA